N:n&#39;-dialkyl-2:2&#39;-dipyrazole-anthronyls and process of making same



Patented July 1 9, 1938 I Y u "UNITED STATES PATENT OFFICE? N :N'-DIALKYL2:2'-DIPYRAZOLE-ANTHRON- I YLS AND PROCESS, OF MAKING SALIE Jakob Koch, Basel, and Max Bommer, Riehen, near Basel, Switzerland, assignors to firmSociety of Chemical Industry in ,Basle, Basel, Switzerland I No Drawing. Application February 19, 1936, Se-

rial No. 64,778. In Switzerland March 8, 1935 Claims. (01. 260- 45) This invention relates to the manufacture of Alternatively, the esters of ethers of polyhydric N:N-dialkyl 2:2Gdipyrazole-anthronyls by inalcohols may be used as alkylating agents, for troducing into a 2-:2 -dipyrazole-anthronyl at example the hydrogen halide esters, the sulfuric least one alkoxy-alkyl-group and, if desired, acid esters and preferably the arylsulfonic acid 5 treating the product obtained by a condensing esters; such esters are, for instance, the mono- 5 and/or substituting agent. chloro-methyl ether (C1CH2OCH3) the chlo- 2:2'-dipyrazole-anthrony1s which constitute roethyl-methyl-ether (Cl-CI-Iz-CHz-OCHs), the parent materials for this invention are, for the diethyl ether of the u-mono-chloro-hydrine example, the 2:2-dipyrazole-anthronyl as Well 7 a as such 2:2'-dipyrazole-anthronyls as contain an 10 alkyl-, for instance methyl-, ethylor benzyle2tt5OeH1-e11-OHT-e1 s q Place the hydrogen Q the as well as the para-toluene-sulfonic acid ester of imino-group of one of the pyrazole 1110161, To m0nd methy1 and t these dipyrazole-anthronyls belong, for example, g1ycO1 the N'meho'ethyl The treatment with the alkylating agent occurs zole-anthronyl. All these parent materials may at a high temperature, f example between 120 Contain in the anthmquimne nucleus of nuclei" and 200 (1; Solutions or diluents, for instance halogens, for 1nstanc e chlorine and bromine, furnitro benzene, hl robenzene', trichlorobenzene, ther alkoxyand nitro-groups, as well as Subamyl-alcohol, naphthalene or anisol-may be used stituted unsubstituted amiuu'groupsin the treatment, and alkylation may be under:

The ihtTPuuetmu of at least one alkoxy'alkyl' pressure or in the open vessel. When unesterified Oup, for Instance methexymethyl', an ethoxy ethers of polyhydric alcohols are used as alkylatmethyl" an ethoxyethylw buthoxyethylj a ing agents, the alkylation is advantageously conbenzyl-hydr0Xyethyl-group, into the 2:2-d py ducted in presence of acid, such as sulfuric acid,

zele-ahthronyl 1S efieeted by any known method; In the use of esters of ethers of polyhydric alco- 25 example by eukylatihg the hydroxyalkylehe hol, the alkali salts; for instance, the sodium and Oup in the 212"uipyrazele-ehthrohyls,in which potassium salts of the 2:2'-dipyrazole-anthronyls the hydrogen atoms of the imino-groups are subare used with advantage Stituted by hyuroxy'alkylehe Sueh as hyurexy' By the invention it is also possible to obtain ethylene, .or by replacing thehalogen in the 2:2'- 1 1 2 dipyrazole anthronyls 3O uipyrazoletehthrouyls, in which hydrogen which are substituted in the-imino-groups by atoms of the imino-groups are substituted by a alkyl-groups which differ from each other; such halogen ellkylenfigroup: such as for lustehee products are obtained, by causing in a first stage chloro-methylene, by the l Y- P for para-toluene-su1fonic acid ester of glycol-mono- Stance by h e e k he methylether to act on the 2:2-dipyrazole-an- 35 '7 However, it is particularly advantageous t p thronyl while in a second stage the para-tolueneuuee the N=N"d1e1k3'1'212"u1pyrem1eehthmhy1s' sulfonic acid ester of the glycol-mono-ethylether by treating t 2ZZ'hiPYTeJZMeauthIPhYIS with is allowed to act, or the dipyrazole-anthronyl such alkylatmg agents wh1ch contaln at least may be treated with mixtures of such alkylating 40 alkoxy-gmup mthe geeky] resluue- Such agents containing alkoxy-alkyl-groups differing'40 t t agents for e e the ethers from each other. Furthermore, such products polyhyerie alcohols which eoutem 'euty one can be obtained by causing the para-toluenesul no e fie hydroxvl-group, for instance the ionic acid ester of glycol-mono-methyl-ether to glyeol'moho'methyl" and acton N-mono-methyl-Z:2-dipyrazole-anthronyl t th t' further the h f ether of or by treating the N-monoa1koxyalkyl-2:2- 45 me y e y -F7 -C -Q dipyrazole anthronylwith a substituting agent,

the uimethy1(eth0xyethy1 searhinol such as methyl halide or ethyl halide.

0H3 cm on: a The 2: 2-dipyrazole-anthronyls obtainable by I a r m con ensin the mono'methyl ether of glycol (hydroxyethyl) agents and/or substituting agents, forflinstanci ether (HO CHZ CH2 OCI:I2 CH2 OCH3) and 'a halogenating agent, whereby further valuable the dimethylether of glycerme products are obtained The new 2:2--dipyrazo1e-anthrony1s may be on V 5 ,,(on o og g V V purified by crystallization or by conversion into their salts with strong acids, or by treatment with oxidizing agents, for instance alkali hypochlorite solution. They may be converted by known methods into the leuco-derivatives, for instance into the leuco-sulfuric acid esters.

The products of theinvention are in part valuable new intermediate products and in part dyestuffs; the latter may be used, if desired, in a admixture with N:N'-dimethylor -diethyl-2:2'- dipyrazole-anthronyls for 'dyeing; and printing vegetable fibres, such as cotton, or for dyeing lacquers and plastic masses, as well as artificial silk, for instance acetate artificial silk. *Insofar as thedyestufis are soluble in'water they may be" used for dyeing animal fibers, for example wool and silk, according to a process used for acid dyestuffs. The dyeings and;printings, particularly those that are red, which they produce, are very fast and, in many cases, change very little intint when the direct dyeing. is developed.

.. .The followingexamplesillustrate the invention,

the parts. being, by weight, unless otherwise is filtered'and boiled alternately with alcohol'and water until the filtrate is practically colourless.

The 'dyestuff is a yellowish red powder. The solution in concentrated sulfuric acid is orange. In a greenish-blue vat cotton is dyed very powerful redtints of excellent; properties of fastness.

= The dyeings are changed Very little by soaping, in

contrast, with those of N:N-diethyl-2:2'dipyrazole-anthronyl, which on soaping turn very strongly to blue red.

Instead of nitrobenzene, ortho-dichlorobenzene or trichlorobenzene may be used as diluent.

Example 2 3 parts of the dry, finely pulverized dipotassium salt of 2:2'-dipyrazole anthronyl are suspended in 70 parts of'nitrobenzene. 14.7 parts of para-toluene-sulfonic 'acid -ester of glycolmono-ethylether are added and the whole .is heated while stirring. At about C. reaction begins and'the color of the mixture changes from brown-to red. Stirringiscontinued for about 16 hours at -160" C. and the whole isthen allowed to cool. The dyestuff thus formed of the formula is mama boiledalternately with llama-Ha 11 parts or the 'potassiuin salt or mono-(N)- water until the filtrate is practically colorless. The dyestuff is then dried. V

The latter is a red powder. The solution in concentrated sulfuric acid is orange. In a greenish-blue'vat cotton is dyed very powerful red tints of excellent properties of fastness. The dyeings practically do not change by soaping.

. Example 3 10.5 parts of'the dipotassium salt of 2:2'-di- 'pyraZole-anthronyl are suspended in 85 parts of trichlorobenzene. 4.5 parts of para-toluenesulfonic acid ethylester are added and stirring is continued for about 1 hours at C. The whole is then allowed to cool to about 80 C. and there are added '7 parts of para-toluenesulfonic acid- ,ester of: glycol-mono-inethyl-ether, whereupon themixture is kept-for a further 12 hours at 160? C. The working up is similar to that described in Example 1. The dyestuff of the probable formula I V V o dissolveslin concentrated sulfuric acid to an orange solution and also yields a greenish-blue vat. Th'ered "dyeings on cotton are of characteris'tic 'fas'tne'ss and are practically unchanged by soapf Theisame dyestuff may be made by a reverse procedure; namely by alkylating first with'the OHaOOH2 -'OHz-NN;

para-'toluenesulfonic acid-ester of. glycol-monomethyl-ether and then'with the para-toluene- Y methyl-ester 'and/orins'tead of the 'para-toluenesulfonic acid-ester 10f glycol-mono .-methylether the para-tolueneesulfonic acid-ester of glycolmono-ethylether may be used for the production of a similar dyestuff."

Example. 4

" 31.5 parts-of dry; finely powdered dipotassium .s'alt' of;2:2'-dipyrazole-anthronyl are suspended :inl 22 5iparts of trichlorobenzene. 15 parts of para-toluenesulfonic acid' ester of glycol-mono- ;methylether are added and stirring is continued for about10 hours at 160C; After cooling, the mono- (N);- methoxy ethyl 2:2 dipyrazoleanthronyl is filtered and-purified by extraction with water andlal'cohol. 1 y

Y '15'partsi'of theiproduct thus obtained :are converted into the'potassium salt." -i

2,124,251 methoxyethyl 2:2 dipyrazole -anthronyl are further 12 hours. The dyestulf thus formed of mixed with 0.5 part of copper acetate and the the formula mixture is heated with 55 parts of ethylbromide in an autoclave for 4 hours at 160 C. After cooling, the dyestuif thus obtained is. purified by extraction with boiling water and alcohol.

The dyestulf is identical with that obtained as described in Example 3.

Example 5 11 parts of N:N'-dimethoxyethyl-2:2-dipyrazole-anthronyl are dissolved in parts of fuming sulfuric acid containing 20 per cent. of S03, 0.1 part of iodine is added and, at about 50? C. '7 parts of bromine are allowed todrop in within about one hour. Stirring is continued for 2 hours at 50-60 C. and then the whole is transferred to ice. The separated dyestuif is filtered, washed neutral and dried. It is a green powder with a bronze lustre which dissolves in concentrated sulfuric acid to an orange solution. Cot- Example 6 10.5 parts of the dry, finely pulverized dipotassium salt of 2:2-dipyrazole-anthronyl are suspended in 85 parts of trichlorobenzene. There are then added 5.1 parts of para-toluenesulfonic acid-ester of glycol-mono-ethylether and the whole is stirred for about 7 hours at C. The mass is then allowed to cool to about 80 C. whereupon 6.9 parts of para toluenesulfonic acid-ester of glycol-mono-methylether are added and the mixture is maintained at 160 C. for a Oil) - is separated by suction and boiled alternately with alcohol and water until the filtrate is practically colorless. The dyestuff is then dried.

The latter is ared powder. The solution in concentrated sulfuric acid is orange. In a greenish-blue vat cotton is dyed very powerful red tints of excellent properties of fastness. The dyeings practically do not change by soaping.

What we claim'is:--

1. N:N'-dialkyl-2:2' dipyrazole-anthronyls of which the'two alkyl groups belong to the lower aliphatic series and at least one of the two alkyl groups represents an alkoxyalkyl group, which products are red powders, soluble in concentrated sulfuric acid to orange solutions and dyeing cotton from a blue colored vat red tints of very good fastness properties. g

2. NzN' dialkoxyalkyl 2:2 dipyrazole an thronyls of which the dialkoxy alkyl groups belong to the lower aliphatic series, which products are red powders, soluble in concentrated sulfuric acid to orange solutions and dyeing cotton from a blue colored vat red tints of very good fastness properties.

3. NzN dimethoxyalkyl-2:2' dipyrazole-anthronyls of which the alkyl groups belong to the lower aliphatic series, which products are red powders, soluble in concentrated sulfuric acid to orange solutions and dyeing cotton from a blue colored vat red tints of very good fastness properties.

4. N:N-dimethoxyethyl 2:2 dipyrazole-anthronyls, which products are red powders, soluble in concentrated sulfuric acid to orange solutions and dyeing cotton from a blue colored vat red tints of very good fastness properties.

5. NzN diethoxyethyl 2 :2 dipyrazole anthronyl of the formula which product is a red powder, soluble in concentrated sulfuric acid to orange solutions and dyeing cotton from a greenish-blue colored vat red tints of very good fastness properties.

' JAKOB KOCH.

MAXBOMMER. 

